Micellization of in situ formed graft copolymers during reactive blending is commonly observed. Numerous studies have been carried out to minimize the formation of micelles and enhance emulsification efficiency. Herein, we investigated the formation of interfacial Janus nanomicelles (JNMs) and their compatibilization effects on immiscible polymer blends when reactive graft copolymers (RGCs) are used as compatibilizers. Poly(styrene-co-glycidyl methacrylate)graft-poly(methyl methacrylate) RGCs were synthesized and used as compatibilizers for immiscible poly(L-lactide) (PLLA)/poly(vinylidene fluoride) (PVDF) blends. Numerous nano micelles were formed in situ during melt blending by grafting of PLLA onto the RGCs. The formation and location of JNMs depended not only on the molecular architecture of the RGCs but also on the melt processing sequence and molecular weight of the components. Interfacial JNMs can effectively improve the miscibility of polymer blends, thereby enhancing the performance of immiscible polymer blends.